Light-sensitive photographic composition



United States Patent Claims priority, application Japan, Aug. 26, 1 965,

- lli/52,123

Int. Cl. G03c 1/72 US. CI. 9690 11 Claims ABSTRACT OF THE DISCLOSURE Alight-sensitive photographic composition comprises, as thelight-sensitive component, an effective proportion of a compound of theformula wherein A is a member of the group consisting of H and Ilii t. Xis a member of the group consisting of O, S, phenyl and phenylsubstituted with lower alkyl; Z is a member of the group consisting ofN, O, S and --N-Y, wherein Y is a member of the group consisting oflower alkyl, aryl and aralkyl; R and R alike or different, are each amember of the group consisting of straight and branchedchain loweralkyl, phenyl, phenylalkyl, substituted phenyl and substitutedphenylalkyl with the phenyl radical substituted with a member of thegroup consisting of lower alkyl, lower alkoxy, halogen, amino,substituted amino, nitro, cyano, and alkoxy carbonyl; R is a member ofthe group consisting of cyano, acyl and alkoxy carbonyl; and R is amember of the group consisting of cyano, alkoxy carbonyl, nitro, acyl,carbamoyl and substituted carbamoyl.

This invention relates to a new light-sensitive, photographiccomposition containing, as a light-sensitive component, a chemicalcompound having a group of the after-specified structure.

It is a principal object of the present invention to provide alight-sensitive composition which is capable of forming a stable imageof the good tone quality by simple procedures and which has goodstability during storage. Some additional advantages and characteristicsof the present invention will be apparent from the followingdescription.

In the prior art of photography, a number of lightsensitive compoundsincluding silver halide compounds, diazo compounds, etc. have been knownand used in various forms. All these known light-sensitive compounds,however, have one or more disadvantages. For example, a light-sensitivephotographic composition which contains silver halide as alight-sensitive component is most widely 3,537,856 Patented Nov. 3, l970 light-sensitive silver halide composition requires complicatedprocedures and equipments. Furthermore silver which is essential as astarting material is very expensive. The actual use of such silverhalide composition usually necessitates a series of wet treatmentsincluding develop ment and fixation. On the otherhand, a light-sensitivediazotype composition although it is inexpensive has poor tone qualityand it also necessitates troublesome wet treatments or use of irritatingammonia vapor. Further it is not so stable during the storage for a longperiod. A binary light-sensitive composition comprising diarylamine andhalogenated hydrocarbon is also well known, which, however, is diflicultto be practically used because the halogenated hydrocarbon is remarkablytoxic.

In accordance with the present invention, there is pro vided a newlight-sensitive composition which is free from the disadvantagesencountered in the prior art. A lightsensitive compound having a groupof the specific structure is rather inexpensive and can be synthesizedby simple procedures. Further, the light-sensitive compound can beeasily prepared as a light-sensitive composition which will yield astable image of the good tone quality through photographic treatments.

Now the present invention will be explained in full detail. Alight-sensitive photographic composition of the present inventioncomprises, as a light-sensitive component, a chemical compound having inits molecular structure a group represented by the formula s} n j lwherein X means oxygen or sulfur atom, and Z means oxygen or sulfur atomor a group =N-Y in which Y is lower alkyl, aryl or aralkyl. Typicalcompounds which are suitable as light-sensitive components in thepresent invention will be generically represented by any one of thefollowing general Formulas I to III wherein Z is oxygen or sulfur atomor a group =NY (in which Y is lower alkyl, aryl or aralkyl), and R and Rhave the same significance as in the above general Formula I. The phenylgroup or groups of the general Formula II are optionally substitutedwith lower alkyl or the like.

R1 1 1 1 N H H X: 2 y X R t R2 R2 (III) wherein X, R R R and R have thesame significances as before.

Typical compounds which fall within the category of the above generalFormula I are as follows:

COMPOUND I 1,3-dibenzyl 6- [cyano (ethoxyearbonyl)methy1] 1,23,6=tetnahydrocycloheptimidazol-'20ne COMPOUND II CH 1's /C I M-P. 143C. HmCsOOC \N M.P. 153 C. HsCzO O C 1,3-dihenzyl-6- [cy-anohexyloxycarbonyl) methyl] 1,2,3,6-tetmhydrocycloheptimidazoLZ-oneCOMPOUND III 1,3-dibenzyl-6-[earbamoylcyanomethyl]-1,-2,3,6-tetrahydrocycloheptimidazol-Z-one COMPOUND IV gradually reddening byheating 1 Q 1,3-dibenzyl-6-dicyanomethyl-1,2,3,6-tetrallydroeycloheptimidazol-2-one COMPOUND V 1,3-dibenzy16-[ethoxycarbonylnltnomethyl] 1,2,3,fi-tetrah drocyeloheptimidazol-z ne C-OzN COMPOUND VI ua. :O

1,3dianisyl-G-dicyanomethyl-l,2,3,G-tetral1ydrocycl0 heptimidazol-Z-oneCOMPOUND VII slow decomposition by heating1,3-dibenzyl6-dieth0xycarbonylmethyl-l2,3,6-

tetrahydrocycl0heptimidaz0l-2-0ne All these Compounds I to VII are newcompounds which have never been disclosed in the known literatures. Theycan be prepared by the reaction of a 1,3-disubstituted-2-0x0-cycloheptaimidazolinium halide of the formula R1 are =0 l (wherein Rand R are the same as defined before and X is halogen or acid residue)with an active methylene compound of the formula (wherein R and R arethe same as defined before) in the presence of a condensing agent. Forillustration, the preparation of the Compound I will be mentioned inExample A.

EXAMPLE A Bis (2-pheny1-(SH-cycloheptoxazol-G-yl) malononitrile COMPOUNDVIII COMPOUND IX N N H (IJN H 3 w I Q 0 i O reddening at O O 0 02115about C.

Ethyl bis (2-phenylGILcyclohept0xazol-G-yl) cyanoacetate COMPOUND Xabout 145 C.

Bis (2-phenyl-6Hcycl0heptoxaz01-Gy1) cyanoacetamide COMPOUND XIreddening at about 142-3 C.

Bis (1-p-tolyl-2-pheny1-1,6-dihydroeycloheptimidazol- 6-5 1)malononitrile These compounds VIII to XIare new compounds and can besynthesized by the reaction of a cycloheptatrienium compound of theformula (wherein X and Z are the same as defined before) with an active,methylene compound of the formula (wherein R and R are the same asdefined before) in the presence of a condensing agent. For illustration,the procedures for the preparation of the Compound VIII will bementioned in Example B.

EXAMPLE B To 0.8 g. of metallic sodium dissolved in 100 ml. of ethanolare added 2.1 g. of malononitrile and 10 g. of2-phenyl-oxazolo-tropilium monomethyl sulfate. The resiilting solutionis stirred at room temperature for 6 hours. The separated crystals arecollected by filtration and washed with ethanol. The mass is added withchloroform and washed with water twice. The chloroform layer is driedover anhydrous sodium sulfate. Then it is treated .with active carbonand concentrated at a bath temperature of not more than 50 C. underreduced pressure. The crystalline residue is added with benzene and thenseparated by filtration. 5.0 g. of bis(2-phenyl-6H-cycloheptoxazol-6-yl)malononitrile is obtained.

'Typical'compound belonging to the category of the general Formula IIIis as follows:

COMPOUND XII N-methyl-bis (1,3-dibenzy1-1,2,3,6 tetrahydro cycloheptimidazo1-2 n-6-yl) eyanoacetamide The preparation of this compoundXIII will be govern in Example'C.

EXAMPLE C To 0.2 g. of metallic sodium dissolved in 40 ml. of ethanol isadded 0.72 g. of cyanoacetic methyl amide. To the solution is then added3.0 g. of 1,3-dibenzyl-2-oxocycloheptaimidazolinium chloride dissolvedin 50 ml. of ethanol. The mixture is stirred at room temperature for 5hours. After standing the mixture overnight, it is filtered to removeundissolved matters. The filtrate is concentrated under reducedpressure. The oily residue is dissolved in ethyl acetate and theresulting solution is passed through a column packed with alumina. Thenthe solution is concentrated and the residue is recrystallized fromcyclohexane to obtain 1.0 g. of N-methyl-bis-(l,3-dibenzyl 1,2,3,6tetrahydrocycloheptimidazol 2 on 3-y1)- cyanoacetamide, M.P. 7 C.

The above-referred compounds can develop color when they are exposed toultraviolet irradiation, and accordingly, a composition which containsone or more than two of these compounds is useful as a light-sensitivecomposition in the photographic art. As is well known to those skilledin the art, the light-sensitive composition with which the inventionconcerns may additionally comprise one or more auxiliary components toimprove the properties of the composition. For example, alkanol amines(e.g. triethanol amine), polyalkylene oxide compounds, etc., can be usedas effective sensitizers to increase the light sensitivity of thecomposition. Other suitable sensitizers include phenyl urethane,acrylamide, acetanilide, o-acetanisidide, diphenyl carbazide,benzalazine, maleic anhydride, phthalic anhydride, succinic anhydride,tartaric anhydride, potassium bichromate, etc. Incorporation of anaromatic amino or nitro compound as auxiliary component serves tocontrol the color tone of the image resulting from ultravioletirradiation of the composition. For example, phthalic, oxalic, benzoic,tartaric and malonic acids or their anhydride,m-hydroxydimethyl-aniline, methyl m-nitrobenzoate, 2-nitrohydroquinonemethyl ether, etc. are suitable color-controlling agents.Diaminostilbenesulfonic acid or the like known optical whitening agentis effective to improve visible whiteness of the background of theimage. Many other auxiliary components can be suitably selecteddepending on the purposes with reference to the known photographictechniques.

In the actual use of a light-sensitive photographic composition of thepresent invention, it is convenient to prepare the composition in theform of a light-sensitive layer coated on a support. Suitable supportsinclude papers, cloths, film bases, metallic plates, etc. Generally,papers and film bases are suitable. For convenience, the term, alight-sensitive element, will be used hereinafter to mean alight-sensitive composition of the invention which is in the form of alayer coated on a support. Such lightsensitive element as referred toabove can be prepared in several ways. Most simply, the light-sensitivecomposition which contains the light-sensitive compound together with orwithout any auxiliary compound is finely divided and then uniformlyrubbed onto the surface of paper or the like support by means of buffrolls. In small scale preparation, the fine particles of thelight-sensitive composition is rubbed onto the surface of paper by usingabsorbent cotton or soft cloth lump. More practically, however, it isadvantageous to dissolve or disperese the lightsensitive component (andthe auxiliary component), together with or without a binder, in anappropriate solvent and then coat the resulting solution or dispersionon a suitable support. Almost all of the light-sensitive compoundsusable in this invention are soluble in ketones such as acetone ormethyl ethyl ketone, acid esters such as ethyl acetate or butyl acetate,and cyclic oxy-hydrocarbons such as dioxane or cyclohexanone, and so,any one of these solvents can be conveniently used for preparation of asolution. On the other hand, water or an alcohol is suitable forpreparation of a dispersion of the light-sensitive compound because thecompound is sparingly soluble in these solvents. In film coating, use ofa binder in combination with the light-sensitive compound is preferable.In coating of the solution containing the light-sensitive compound, afilm-forming polymeric material which is well soluble in the solventused is suitable as a binder. Typically usable are acrylic resin;polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinylbutyral or the like polyvinyl resin; and cellulose acetate, ethylcellulose or other cellulose derivatives. For dispersion type coating,suitabe binders are water-soluble, alcohol-soluble polymeric materialsincluding gelatine, gum arabic, polyvinyl alcohol, carboxymethylcellulose, etc. In the preparation-f the coating solution, alightsensitive compound and, if desired, an auxiliary compound aresimply dissolved in a suitable solvent in which a binder has beendissolved. If the coating dispersion is to be prepared, alight-sensitive compound is ground with a small amount of acetone or thelike and then the resulting mass, added with an aqueous gelatine, istreated by means of an ultrasonic disperser, ball mill, micron mill orthe like, thereby to have desired dispersion. The coating solution ordispersion thus prepared can be applied onto a support by any proceduresknown per se in the art. Coating of the light-sensitive compound in theamount of 0.5- grams per square meter of the support is preferred.Generally, a light-sensitive element produced by rubbing of the fineparticles of a light-sensitive compound or by using a dispersion of thelight-sensitive compound yields a stable image with high contrast,whereas a lightsensitive element produced by using a solution of thelight-sensitive compound yields a vividly colored image of the good tonequality which makes the composition adaptable to use in the reproductionof an image from a continuous tone photographic negative.

Imagewise exposure of the light-sensitive element to ultravioletirradiation gives a color image which, when heated, is fixed with anincrease of color density, to have good stability against further lightexposure. The colored image thus obtained is of fine grain and highresolution, and it is stable during the long period of storage. In thepractical use of the light-sensitive element, all the procedures areconducted in dry process not involving use of any liquid agent. Thus,the said element can be easily used without special care. In theparticular embodiment using a light-sensitive element of the dispersiontype coating, however, fixation by solvent treatment also is applicable.Further it is noted that reversal development of such light-sensitiveelement as above is possible.

As a light-sensitive element of the invention can develop color by lightexposure, it is useful in so-called negative-positive method. Thus if apositive image is desired an original having a negative image should beemployed. In a particular case, however, wherein excessive lightexposure is given, reversal phenomenon which is alike solorization in asilver photographic process takes place so that the light-sensitiveelement is usable in the manner of a positive-positive method. As lightexposure, ultraviolet irradiation is most eflicient. A mercury lamp, arclamp, high power fluorescent lamp, etc. are recommended as light source.However, as far as sufficient illumination is assured, a usualincandescent lamp can be used in combination with a slide projector. Thelight-sensitive element thus exposed is then heated up to 100- 150 C.thereby to eifect fixation with simultaneous increase in image density.Heating may be elfected by various means. For instance, thelight-sensitive element is passed at a speed of about 5 cm./sec. betweenhot rolls having a surface temperature of about lOO-l30 C. Insertionbetween two uniformly heated platens also is possible. Furtheralternatively, use of a hot air (120 C.) chamber or irradiation from aninfrared lamp is acceptable for the purpose of fixation. In case of alightsensi tive element of the dispersion type coating, solventtreatment may be made instead of heating, with the result of imagefixation and increase of color density. For example, an organic solvent,such as pyridine, tetrahydrofuran, n-propyl alcohol, etc., to which isadded an optional amonut of water to control the dissolving power ofsaid solvent, is used to treat the light-sensitive element having beenprinted.

The following examples describe certain ways in which the principle ofthe invention has been applied, but are not to be construed as limitingits scope.

EXAMPLE 1 45 grams of a polystyrene resin Stylon (registered trade name,manufactured and sold by Dow Chemical Corp., USA.) is dissolved in 1liter of methyl ethyl ketone. To the resulting solution is added 30 g.of the above-indicated compound (I) as light-sensitive component. AfterWell agitation, a light-sensitive solution is obtained, which is coatedat the amount of 50 ml./m. on a photographic baryta paper and thendried. All the procedures mentioned above are carried out under yellowphotographic safe light in a dark room, avoiding invasion of daylight.

The light-sensitive element thus prepared is superposed with aphotographic negative bearing an original image and the resultingcomposite is exposed to irradiation from 1 kw. high pressure quartzmercury lamp for 5 seconds. Through a photochemical reaction which takesplace in the exposed area of the element is formed a pale image. Theelement is then passed at a speed of 5 cm./sec. between hot rolls havinga surface temperature of 120 C., thereby to effect fixation of the imagewhile image density is remarkably increased. The resulting red-orangecolored positive image has good tone quality and is so stable that itdoes not show any appreciable change even after one hour exposure todirect sunlight.

.By utilizing so-called reversal phenomenon, the same light-sensitiveelement can be used for obtaining reproduction of the positive-positivetype. For instance, the light-sensitive element is superposed with atracing paper bearing handwritten original and the composite is subectedto irradiation from a mercury lamp for one minute. Thereafter, theelement is heated by means of 120 C. hot rolls. A clear positive copy ofthe original is obtained.

Other light-sensitive elements can be prepared by repeating theabove-mentioned procedures excepting that the equal amount of thecompound (II), (HI), (X) or (XII) is used in place of the compound (I).The image color shade and specific speed of these light-sensitiveelements produced thereby are as follows:

Specific Color shade speed, of image index Compound:

(I) (II)- 100 (III) 50 (IX) Orange 10 (XII) do--. 50

EXAMPLE 2 The light-sensitive solution as prepared in Example 1 iscoated on a 0.12 mm. thick polycarbonate film base Konifoil C (tradename of Konishiroku Photo Industry Co., Ltd., Japan) and then dried. Thelight-sensitive film thus prepared is superposed with a photographicnegative and then the composite is exposed in the same manner as inExample 1. After working up the film in the same manner as in Example 1,a transparent positive image is obtained, which is of no grain and hashigh resolution. A clear visible image is observed on a screen when theoriginal image is projected at any desired magnification by means of aslide projector. The light-sensitive film of this example is useful forpreparation of original slide plates or reproduction of microfilms.

EXAMPLE 3 The compound (X) is uniformly rubbed at the amount of 2 g./m.onto the surface of a coated paper by using absorbent cotton. Thelight-sensitive paper thus prepared is treated in the same manner as inExample 1. After printing (imagewise exposure) and thermal fixation, a

EXAMPLE 4 In a 2 litre-volume beaker, 30 g. of the compound (I) and 100ml., of acetone are thoroughly mixed to form a pasty mass, to which isadded 1 litre of a 4.5 aqueous gelatin solution. The total mass is thentreated by means of a ultrasonic type homogenizer, Model USH-15Q(manufactured and sold by Ultrasonic Industry Co., Japan) to have alight-sensitive dispersion containing the fine particles of thelight-sensitive component in gelatine. This dispersion is coated at theamount of 50 ml./m. onto the surface of a photographic baryta paper andthen dried. The light-sensitive element thus prepared is treated in thesame manner as in Example 1', thereby to obtain a clear positive imagefrom a photographic negative. The light-sensitive element used in thisexample is characterized by that it gives an image which is higher indensity and contrast and more vivid in tone quality than the imageobtained in Example 1.

An alternative procedure for fixation of the-image obtained by using thelight-sensitive element of this example is solvent treatment. For thispurpose, the light-sensitive element bearing a pale image after printingis treated with a mixture of tetrahydrofuran and water (1:1) for severalten seconds, whereby fixation is completed with increasing imagedensity. The fixed image is now stable even under daylight.

EXAMPLE 5 45 grams of polystyrene resin is dissolved in 1 l. of methylethyl ketone, and to the resulting solution are added g. of theabove-indicated compound (XII) as light-sensitive component and 60 g. ofm-dimethylaminophenol as image color-modifying agent. The .resultingmixture is well stirred to have a light-sensitive solution, which isthen coated at the amount of 50 mL/m. on a photographic triacetate filmbase. The light-sensitive element thus prepared is superposed with aphotographic negative and the resulting composite is exposed toultraviolet irradiation from a 1 kw. mercury lamp for 10 seconds.Thereafter, the light-sensitive element is passed at the speed of 5cm./sec. between hot rolls having a surface temperature of 120 C.,thereby to effect fixation with an increase of image density. Theresulting purplecolored, dense image is of non-grain and of highresolution and has good tone quality and satisfactorily high density.The image can be clearly seen on a screen by enlarged projection. If theprocedures given in this example are repeated with exception of additionof the m-dimethylaminophenol, the image obtained thereby is orange incolor and has insufficient density to effect production.

EXAMPLE 6 In a 2 litre-volume beaker, g. of the compound (I) aslight-sensitive component and 100 ml. of acetone are well mixed to forma paste, to which are then added 1 litre of 4.5% aqueous gelatinesolution and 5 ml. of 2% Teepol (trademark of Shell Chemical Co.,U.S.A.; alkyl sulfate type anionic type surfactant). The total mixtureis treated by means of an ultrasonic homogenizer to obtain a dispersionhaving the light-sensitive component dispersed therein. To thedispersion, 4 ml. of triethanol amine (sensitizer), 10 ml. of 1%mucochloric acid (gelatine hardener) and 8 ml. of 2% Leucophor(trademark of Sandoz Ltd, Switzerland; diaminostilbene sulfonic acidtype optical whitening agent) are added. The mixture is thoroughlymixed. The light-sensitive dispersion thus prepared is coated at theamount of 50 mL/mfi on a photographic baryta paper and then dried.

The light-sensitive element thus obtained is used in the same manner asin Example 1. From a photographic negative, a clear, reddishorange-colored positive image is obtained. As the result of addition ofthe sensitizer,

the element of this example is twice faster in photographic speed thanthe'light-sensitive element of Example 1. Further, addition of theoptical whitening agent results in improvement in whiteness of thebackground so that the image may be very clearly visible.

What we claim is:

1. A light-sensitive photographic composition which comprises, as thelight-sensitive component, an effective proportion of a compound of theformula I wherein A is a member of the group consisting of H and R1 V p:

Z V I ka X is a member of the group consisting of O, S, phenyl andphenyl substituted with lower alkyl; Z is a member of the groupconsisting of N, O, S and -N-Y, wherein Y is a member of the groupconsisting of lower alkyl, aryl and aralkyl; R and R alike or different,are each a member of the group consisting of straight and branched-chainlower alkyl, phenyl, phenylalkyl, substituted phenyl and substitutedphenylalkyl with the phenyl radical substituted with a member of thegroup consisting of lower alkyl, lower alkoxy, halogen, amino,substituted amino, nitro, cyano, and alkoxy carbonyl; R is a member ofthe group consisting of cyano, acyl and alkoxy carbonyl; and R is amember of the group consisting of cyano, alkoxy carbonyl, nitro, acyl,carbamoyl and substituted carbamoyl.

2. The light-sensitive, photographic composition of claim 1 whichcomprises, as the light-sensitive component, a member of the groupconsisting of compounds havin the formulae:

1?: R3 H H N \i R4 N I M (I) N H Rs H N i y-K) Z R Z (II) and 1 R1 1%11: J O l C- 0 I ia I ia (III) with the proviso that when the compoundis of Formula III R represents a cyano group and R represents asubstituted carbamoyl group and that when the compound is of Formula IR; does not represent a substituted carbamoyl group.

3. A composition according to claim 2 wherein the light-sensitive agentis 1,3-dibenzyl-6-[cyano(ethoxycarbonyl)methyl] 1,2,3,5tetrahydrocycloheptimidazol-1-2- one; 1,3-dibenzyl-6- [cyano(hexyloxycarbonyl) methyl] 1 2,3,6 tetrahydrocycloheptimidazol 2-one;3-dibenzyl-6- (carbamoylcyanomethyl) 1,2,3,6 tetrahydrocycloheptimidazol2 one; 1,3 dibenzy1-6-dicyanomethyl-1,2,3,6- tetrahydrocycloheptimidazol2 one; 1,3-dibenzyl-6-(ethoxycarbonylnitromethyl) 1,2,3,6tetrahydrocycloheptimidazol 2-one; 1,3di-p-anisyl-6-dicyanomethyl-1,2,3,6-tetrahydroxycycloheptimidazol-2-one; or 1,3-dibenzyl-6-diethoxycarbonylmethyl 1,2,3,6-tetrahydrocycloheptirnidazol-2-one.

4. A composition according to claim 2 wherein the light-sensitive agentis bis(2-phenyl-6H-cycloheptoxazol- 6-yl)malononitrile; ethyl bis(2-phenyl-6H-cycloheptoxazol-6-yl)cyanoacetate; bis(2-phenyl-6H-cycloheptoxazol- 6 -yl) cyanoacetamide; or his(1-p-t0yly-2-phenyl-1,6-dihydrocycloheptimidazol-6-yl -malononitrile.

5. A composition according to claim 2 wherein the light-sensitive agentis N-methyl-bis (1,3-dibenyl-1,2,3,6-tetrahydrocycloheptimidazol-Z-on-6-yl) cyanoacetamide.

6. A light-sensitive, photographic composition as claimed in claim 1,wherein the composition is present in the form of a light-sensitivelayer supported on a support.

7. A light-sensitive, photographic composition as claimed in claim 6,wherein said layer further comprises a sensitizer, a color-controllingagent and/or an optical whitening agent.

8. A light-sensitive, photographic composition as claimed in claim 7,wherein said sensitizer is selected from triethanol amine, phenylurethane, acrylamide, acetanilide, o-acetanisidide, diphenyl carbazide,benzalazine,

maleic anhydride, phthalic anhydride, succinic anhydride, tartaricanhydride, polyethylene oxide and potassium bichromate.

9. A light-sensitive, photographic composition as claimed in claim 7,wherein said color-controlling agent is selected from phthalic, oxalic,benzoic, tartaric and malonic acids and their anhydrides,m-hydroxydimethylaniline, methyl m-nitrobenzoate and 2-nitrohydroquinonemethyl ether.

10. A light-sensitive, photographic composition as claimed in claim 1,wherein the composition is in the form of a solution in which saidlight-sensitive compound, together with a film-forming binder selectedfrom the group consisting of polystyrene, polyvinyl chloride,polyvinylidene chloride, polyvinyl butyral, acetyl cellulose, and ethylcellulose is dissolved in an organic solvent therefor.

11. A light-sensitive, photographic composition as claimed in claim 1,wherein the composition is in the form of a dispersion in which saidlight-sensitive compound, together with a water-soluble polymeric binderselected from the group consisting of gelatine, gum arabic, polyvinylalcohol, and carboxymethyl cellulose is dis persed in water.

References Cited UNITED STATES PATENTS 5/1968 Willems et a1. 9690 X7/1964 Stewart et a1 96-90 X US. Cl. X.R.

